Hardened artificial materials and process of preparing them



ible resins containing 0 Patented May 31, 1932 i v sumran s r'rss PATET orFIca ARTHUR V038, 0F FRANKFOBT-ON-THE-IM.AIN-HOCHST, GERMANY, ASSIGNOR TO I. FABBENINDUSTRIE AK'IIENGESELLSGHAFQ OF .FBANKFORT-ON-THE-MAIN, GER- may HARDENED ABTTFICIAL MATERIALS AND PROCESS OF PREPARING THEM:

Ho Drawing. Original application filed September 19, 1928, Serial No. 507,042, and in Germany September 29, 1927. Divided and this application filed. January 7', 1930. Serial No. 419,191.

M present invention relates to hardened artificial materials and process of preparing them, more particularly to materials consisting of or containin insoluble and infusemically entirely indifferent carboxyl groups.

The aforesaid resins containing carboxylic acid groups (hereinafter referred to for convenience as resin-carboxylic acids) may 10 be obtained by reaction between a'phenolaldehyde resin and a halogen fatty acid or a salt thereof, or by reaction between a phenoxyfatty acid and formaldehyde or a substance yielding formaldehyde. I have moreover is found that insoluble and infusible resins are obtained by transforming the said resins containing carboxyl groups in water-soluble compounds b neutralizing them wholly or partially wit. ammonia or the derivatives thereof, as, for instance, methylamine or pyridine, then evaporating the aqueous solution and heating the residue at a temperature between 100 C. and 200 C., preferably at about 150 C. to 160 C- If desired, a filling material may be associated with the aqueous solution of the ammonium or other salt of the resin-carboxylic acid. New artificial materials may, for instance, be made by impregnating paper-pulp 80 with the aqueous solution, pressin into a entirely water a. are intende suitable mould and hardening by eating. By impregnating wood-paste which is obtainable cheaply in. commerce, with the solu tion, it is thus possible to manufacture molded articles of any shape, such as pipes, boxes,

barrels, and other various-kinds of articles of general utility. Artificial masses may also be made by impregnating paper web, superposing a number 7 of layers of theimpregnating web, and subse uently hardening the mass.

e molded articles thus obtained {have valuable propertiesin articular, the are roo an 'extraordinari y resistant to men anical and chemical action. According to the (purpose for which the prod- V v V there'may be used instead of a paper-pulp or web another filling material, such as asbestos fibers, sawdust infusorial earth, powdered born or the polyvinyl alcoho Theproducts have a'low electrical conductivity, and are, therefore, well suited for electrical insulation. The are also applicable as substitutes for shel ac and the manufacture of stiifenings for hats or caps.

By a further feature of the invention, the

resin-carboxylic acids may be converted into od of operating, it is even possible to dispense a carbohydrate soluble in with the conversion of the resin-carboxy1ic acid into its salt, andi the invention accordingly includes a manufacture of hardened artificial material by heating a resin-carboxylie acid at a temperature at above C. n

the presence of a polyhydric alcohol of low volatility, with or without addition of a filling material,'for example, the resin-carboxylic acid is dissolved in alcohol, the solution is mixed with a quantity of glycerine, equi molecular to that of the resin acid, or an equimolecular quantity of another polyhydric alcohol of low volatility, such as pentaerythritol, the solution is evaporated and the residue hardened as already described. In some cases, the solvent may.be dispensed with, it being suificient merely to mix the resin-carboxylic acid and the polyh cohol, and to heat the mixture to t e necessary temperature.

dric al-.

Products of particularly good elasticity are Q as the polyvalent alcohol obtainable by saponification of olyvinyl acetate.

The ollowingexamples illustrate the invention, the parts being by weight: I

(1) parts of the artificlal'resin obtainable by reaction between parts of formaldehyde of 30 per cent. strength and 110 parts of commercial cresol in the presence of an alkali, are dissolved in 250 parts of concentrated caustic soda solution (42 B.) and 260 parts of water. Into the clear, somewhat obtained by usin is preci viscous solution 90 arts of chloracetic acid are introduced slowly-in portions at a temperature between 50 and60 C. The introduction of eachportion causes spontaneous evolution of heat and in order to avoid frothing the temperature is controlled so that it doesnot exceed 80 C. When all the chloracetic acid has been introduced the temperature is maintained for about minutes at 100 C. to 102- C. The clear solution is diluted with several times its volume of water and the resin-carboxylic acid thus obtained itated by the addition of hydrochloric aci until the mass is acid in reaction. The resin acid is freed by washing from salt and other inorganic bodies. The paste thus obtained is introduced whilst still moist into I I applied to surfaces and an aqueous solution of ammoniaat a moderately raised tem erature, preferably about C.- C. be strength and quantity of the solution are such that the quantity of ammonia used is equivalent to that of the resin acid, and amounts to about 17 parts of NH,; a smaller quantity of ammonia is however suflicient for obtaining a clear solution, which by reason of the presence of free carboxylic acid has an acid reaction. The acid or neutral solution may be used directly as such or it ma be concentrated or diluted in any desired egree. It may be used for im regnating paperulp, or animal or vegetab e tissues; it is a 0 suitable for preparing lacquers because the solution is easily ields on dryin a smooth lustrous film, w ich when heate .to about 150 0. becomes infusible andinsoluble. In order to obtain the product in an anhydrous solid state it is suflicient to evaporate thesolution advantageously in a vacuum for the ur ose of avoiding overheating. The sully rous product is a dry owder whichlikewise becomes insoluble and infusible, with separation of ammonia and water vapour when heated to a temperature above 100 C. It is easily soluble in water and has, as compared with the artificial resin known as bakelite the advantage that for the Preparation of solutions the use of relative y expensive organic solvents may be avoided.

(2) The resin-canboxylic acid prepared as described in Examfle 1 is dissolved in an aqueous solution 0 yridine instead of in aqueous ammonia. 'Fhe hardened products obtainable from this solution in the manner already described are more elastic than those obtained as described in Example 1 but less resistant to chemical action.

(3) The resin-carboxylic acid obtainable by reaction between 30 parts of paraformaldehyde and 100 parts of cresoxyacetic acid in the presence of hydrochloric acid is freed from electrolytes by washing and then dissolved in 300 parts of an aqueous solution of methylamine of 8 per cent strength. The socondensation of equal lution may be used in the manner described in Example 1, for impregnating materials, for the preparation of lacquers, and for the manufacture of artificial objects.of various kinds. p

(4) The resin-like product obtained by arts of commercial tricresol and formalde yde of 30 per cent strength in the presence of aboutlO per cent of an alkali is mixed, without being freed from the alkali used for the condensation, with a quantit of a concentrated aqueous solution of an a kali such that the total quantity of the alkali present is equivalent to the quantity of the cresol used. Into the clear aqueous solution thus obtained there is introduced in the form ofa concentrated aqueous solution, a quantity of sodium chloracetate also equivalent to the cresol used, at a temperature of about 60 C.7 0 C. To a condensa-' tion product obtained from 108 arts of oresol, 108 parts of formaldehyde 0 30 r cent. strength and 30 parts of concentrate caustic soda solution of 42 B., there are added to a moderate temperature (40 C.50 C.) a fur-' ther 90 parts of caustic soda solution and 116.5 parts of sodium chloracetate', the whole being maintained at about 40 C.50 C. until all sodium chloracetate has been introduced, after which it'is heated for a short time at 95 G.-100 C. for the purpose of accelerating the reaction. The resin-acid product is precipitated by acidification with ydrochloric acid; it is a whitish resinous mass which when cold easily crumbles, but becomes soft at a moderately raised temperature. It is washed, dissolved in 400 parts of warm aqueous ammonia of 10 per cent. strength, and the clear, feebly colored solution produced which has a slightly ammoniacal smell, is mixed with an a ueous solution of 25 parts of polyvinyl a cohol. After evaporating the solution thus obtained on a water bath, there remains a clear resinous residue, WhlOh when further heated to about 150 C.-170 G. gradually becomes converted into a hard mass which is entirely insoluble and infusible, but nevertheless very elastic; it may conveniently be used for the pre .aration of articles WhlCh are required to resistant toward thrust or other mechanical action.

- (5) 100 parts of the phenol-formaldehyde condensation product known as bakelite A,

are caused to react in the manner already de-' scribed with chloracetic acid and the resinacid thus obtained is dissolved in aqueous amnionia as described in Example 4. The a ueous solution is mixed with 15 parts of g ycerine of 97 r cent. strength, the mixture is kneaded a uantity of paperulp of 22 per cent. strengt such that a uni orm pasty mass is produced. The mass is freed from a partof the solution by pressing, the solid cake thus obtained is pressed in suitable 7 307,042, filed September 19, 1928, which has matured into Patent No. 1,805,385.

I claim: 1. The process which comprises treating.

phenolaldehyde condensation products con-.

taining carbonyl groups with a nitro en base selected from the group consisting o ammonia, aliphatic amines and cyclic amines and heating the water-soluble compounds thus obtained to a temperature of between 100 C. and 200 C.

2. The recess which. comprises treating condensation products obtained from a phenolaldehyde resin and a halogen fatty acid with a mtrogen base selected from the group consisting of ammonia, aliphatic aminesand cyclic amines and heating the'water-soluble compounds thus obtained to a temperature of betweeen 100 C. and 200 C.

3. The process which comprises treating condensation products obtained from the condensation product of phenol and formaldehyde and chloracetic acid with a nitrogen base selected from the group consisting of ammonia, aliphatic amines and cyclic amines and heating the water-soluble compounds thus obtained to a temperature ,of between 100 C. and 200 C. I 4. The process which comprises treating phenolaldehyde condensation products containing carboxyl groups with ammonia and ferent carboxyl grou s' an tical with resins obtai inible by treating phe- I ble. resins containing chemically entirely in-- heating the water-soluble compounds thus obtained to a temperature of between 100 C. and 200 C. Y

5. The process which comprises treating condensation products obtained fromthe condensation product of phenol and formaldehyde and chloracetic acid with ammonia and heating the water-soluble compounds thus obtained to a temperature of between 100 C. and 200. C. i

6 As newproducts, insoluble and infusible resins contammg 'chemicall entirel indifnolaldehyde condensation products contaming carbonyl groups witha nitro 11 base selected from the group consisting o ammon1a,,k aliphatic amines and cyclic amines and heat ng the water-soluble compounds obtained to a temperature of between 100 C. and 200 C; .0

7. As new products, insoluble andfinfusidifierent c'arhoxyl oups, substantially identical with tainable b treating condensation products obtained in a p as y identhus bis resins containing chemically entirel indifierent carboxyl groups, substantially identical with resins obtainable by treating condensation products obtained from the condensation product of. phenol and formaldehyde and chloracetic acid with a nitrogen base selected from the group consisting of ammonia, aliphatic amines and cyclic amines and heating the water-soluble compounds thus obtained to a temperature of between 100 C. and 200 C. I Q

9. As new products, insoluble and infusible resins containing chemically entirely in difierent carboxyl groups, substantially 1dentical with resins obtainable by treating phenolaldehyde condensation products containing' carboxyl groups with ammonia and heating the water-soluble compounds thus obtained to a temperature of between C.

10. As new products insoluble and b le resins containing chemicall'yentirely in-' difierent carboxyl identical with resins condensation products obtained irom the condensation product of phenol and formaldehyde and chloracetieacid with onia and heating the water-soluble compounds thus obgroups, substantially obtainable by treating tained to a temperature of between 100 C. v

and 200 C.

In testimony whereof, I a Q 

